Scott D. Young

Predicting the activity of Cd2+ and Zn2+ in soil pore water from the radio-labile metal fraction

Abstract Cadmium and zinc were added at 3 and 300 mg kg −1 , respectively, to 23 soils and incubated at 16°C and 80% field capacity for 818 d. Following addition of metal, changes in the radio-labile concentrations of both elements were examined on seven separate sampling occasions over 818 d. At each sample time, soil pore water was extracted using Rhizon soil solution samplers, and concentrations of Cd, Zn, dissolved organic carbon, and major cations and anions were determined. The chemical speciation program WHAM 6 was used to determine free metal ion activity, (M 2+ ). Similar measurements were made on a set of historically contaminated soils from old mining areas, sewage sludge disposal facilities, and industrial sources. The two data sets were combined to give a range of values for p (Cd 2+ ) and p (Zn 2+ ) that covered 5 and 4 log 10 units, respectively. A pH-dependent Freundlich model was used to predict Zn 2+ and Cd 2+ ion activity in soil pore water. Total and radio-labile metal ion concentration in the solid phase was assumed to be adsorbed on the “whole soil,” humus, or free iron oxides to provide alternative model formats. The most successful models assumed that solubility was controlled by adsorption on soil humus. Inclusion of ionic strength as a model variable provided small improvements in model fit. Considering competition with Ca 2+ and between Zn 2+ and Cd 2+ produced no apparent improvement in model fit. Surprisingly, there was little difference between the use of total and labile adsorbed metal as a model determinant. However, this may have been due to a strong correlation between metal lability and pH in the data set used. Values of residual standard deviation for the parameterized models using labile metal adsorbed on humus were 0.26 and 0.28 for prediction of p (Cd 2+ ) and p (Zn 2+ ), respectively. Solubility control by pure Zn and Cd minerals was not indicated from saturation indices. However there may have been fixation of metals to non-radio-labile forms in CaCO 3 and Ca-phosphate compounds in the soils in the higher pH range. Independent validation of the Cd model was carried out using an unpublished data set that included measurements of isotopically exchangeable Cd. There was good agreement with the parameterized model.

Predicting the transfer of radiocaesium from organic soils to plants using soil characteristics

A model predicting plant uptake of radiocaesium based on soil characteristics is described. Three soil parameters required to determine radiocaesium bioavailability in soils are estimated in the model: the labile caesium distribution coefficient (kd1), K+ concentration in the soil solution [mK] and the soil solution-->plant radiocaesium concentration factor (CF, Bq kg-1 plant/Bq dm-3). These were determined as functions of soil clay content, exchangeable K+ status, pH, NH4+ concentration and organic matter content. The effect of time on radiocaesium fixation was described using a previously published double exponential equation, modified for the effect of soil organic matter as a non-fixing adsorbent. The model was parameterised using radiocaesium uptake data from two pot trials conducted separately using ryegrass (Lolium perenne) on mineral soils and bent grass (Agrostis capillaris) on organic soils. This resulted in a significant fit to the observed transfer factor (TF, Bq kg-1 plant/Bq kg-1 whole soil) (P < 0.001, n = 58) and soil solution K+ concentration (mK, mol dm-3) (P < 0.001, n = 58). Without further parameterisation the model was tested against independent radiocaesium uptake data for barley (n = 71) using a database of published and unpublished information covering contamination time periods of 1.2-10 years (transfer factors ranged from 0.001 to 0.1). The model accounted for 52% (n = 71, P < 0.001) of the observed variation in log transfer factor.

Dietary mineral supplies in Africa

Dietary micronutrient deficiencies (MNDs) are widespread, yet their prevalence can be difficult to assess. Here, we estimate MND risks due to inadequate intakes for seven minerals in Africa using food supply and composition data, and consider the potential of food-based and agricultural interventions. Food Balance Sheets (FBSs) for 46 countries were integrated with food composition data to estimate per capita supply of calcium (Ca), copper (Cu), iron (Fe), iodine (I), magnesium (Mg), selenium (Se) and zinc (Zn), and also phytate. Deficiency risks were quantified using an estimated average requirement (EAR) ‘cut-point’ approach. Deficiency risks are highest for Ca (54% of the population), followed by Zn (40%), Se (28%) and I (19%, after accounting for iodized salt consumption). The risk of Cu (1%) and Mg (<1%) deficiency are low. Deficiency risks are generally lower in the north and west of Africa. Multiple MND risks are high in many countries. The population-weighted mean phytate supply is 2770 mg capita−1 day−1. Deficiency risks for Fe are lower than expected (5%). However, ‘cut-point’ approaches for Fe are sensitive to assumptions regarding requirements; e.g. estimates of Fe deficiency risks are 43% under very low bioavailability scenarios consistent with high-phytate, low-animal protein diets. Fertilization and breeding strategies could greatly reduce certain MNDs. For example, meeting harvestplus breeding targets for Zn would reduce dietary Zn deficiency risk by 90% based on supply data. Dietary diversification or direct fortification is likely to be needed to address Ca deficiency risks.

Characterizing the availability of metals in contaminated soils. I. The solid phase: sequential extraction and isotopic dilution

The two approaches most commonly applied to characterizing the chemical form and ‘reactivity’ of metals in the soil solid phase are sequential extraction procedures (SEPs) and isotopic dilution (ID). The development and limitations of both approaches are described and their application to contaminated soils discussed. It may be argued that ID offers a better means of discriminating between ‘reactive’ and ‘inert’ forms of metal. However, the literature on SEPs is considerably larger, providing greater scope for comparative analysis of new data. Although ID methods are subject to operational constraints, the procedural dependency of SEPs is probably much greater. Thus greater effort has been expended to standardize and verify methodologies for SEPs. However, despite achieving a level of ‘political ratification’ at the procedural level, the use of SEPs within risk assessments for planning or development purposes is currently almost absent. The future for ID methods in this context may lie in site-specific risk assessments that include improved methods for the prediction of metal solubility and bioavailability.

Evaluating a free ion activity model applied to metal uptake by Lolium perenne L. grown in contaminated soils.

We investigated several formulations of the ‘free ion activity model’ (FIAM) as a means of describing plant uptake of soil Cd and Zn from contaminated soils. Lolium perenne was grown on a range of urban and metal-spiked agricultural soils selected to provide a wide range of Cd and Zn concentrations, pH values and other physico-chemical properties. Plants were grown under controlled conditions and above-ground biomass was harvested at regular intervals. Concentrations of Cd and Zn in the grass were compared with estimates of metal ‘capacity’ (total or radio-labile metal content in the soil) and ‘intensity’ (metal concentration in the soil solution or free divalent ion activity). The results suggested that ‘capacity’ terms alone were poor predictors of plant metal uptake (r2 values between 0.001 and 0.43), while metal ion ‘intensity’ provided quite reasonable predictions of the variation observed for several harvests of the grass (r2=0.60–0.87). Soil solution-to-plant transfer factors were highly pH-dependent which may suggest significant competition between trace metals and protons for sorption sites on roots. However, resolution of this question was confounded because of the strong co-variance between pH and p(M2+) in the soil pore water. Thus the influence of pH could not be separated from the effect of changing metal ion activity on uptake rate. Other possible effects on metal uptake such as dilution from increased biomass during growth and competition for uptake between different metal ions (Zn vs. Cd), or with Ca2+, appeared to play very minor roles in determining bioavailability. Several formulations of the FIAM failed to provide a consistently superior prediction of metal uptake when compared to purely empirical regression with pH and p(M2+) within the range of the data used to parameterise the models.

Dietary calcium and zinc deficiency risks are decreasing but remain prevalent

Globally, more than 800 million people are undernourished while >2 billion people have one or more chronic micronutrient deficiencies (MNDs). More than 6% of global mortality and morbidity burdens are associated with undernourishment and MNDs. Here we show that, in 2011, 3.5 and 1.1 billion people were at risk of calcium (Ca) and zinc (Zn) deficiency respectively due to inadequate dietary supply. The global mean dietary supply of Ca and Zn in 2011 was 684 ± 211 and 16 ± 3 mg capita−1 d−1 (±SD) respectively. Between 1992 and 2011, global risk of deficiency of Ca and Zn decreased from 76 to 51%, and 22 to 16%, respectively. Approximately 90% of those at risk of Ca and Zn deficiency in 2011 were in Africa and Asia. To our knowledge, these are the first global estimates of dietary Ca deficiency risks based on food supply. We conclude that continuing to reduce Ca and Zn deficiency risks through dietary diversification and food and agricultural interventions including fortification, crop breeding and use of micronutrient fertilisers will remain a significant challenge.

Maize grain and soil surveys reveal suboptimal dietary selenium intake is widespread in Malawi.

Selenium is an essential element in human diets but the risk of suboptimal intake increases where food choices are narrow. Here we show that suboptimal dietary intake (i.e. 20–30 µg Se person−1 d−1) is widespread in Malawi, based on a spatial integration of Se concentrations of maize (Zea mays L.) grain and soil surveys for 88 field sites, representing 10 primary soil types and >75% of the national land area. The median maize grain Se concentration was 0.019 mg kg−1 (range 0.005–0.533), a mean intake of 6.7 µg Se person−1 d−1 from maize flour based on national consumption patterns. Maize grain Se concentration was up to 10-fold higher in crops grown on soils with naturally high pH (>6.5) (Eutric Vertisols). Under these less acidic conditions, Se becomes considerably more available to plants due to the greater solubility of Se(IV) species and oxidation to Se(VI).

Characterizing the availability of metals in contaminated soils. II

Abstract. Methods that can be used to determine the distribution of metal species in soil solution are critically reviewed and assessed. They are divided into two groups: those that can provide free ion activity, and those that measure labile species in solution. Ion selective electrodes have long been regarded as a promising technique, but there are practical problems in performing accurate measurements and only the Cu electrode has been used routinely. The Donnan membrane technique is capable of measuring the free ion activity of many metals, but adequate sensitivity can be a problem. Although resin competition methods are versatile, care must be exercised to avoid perturbing the solution excessively. Anodic stripping voltammetry (ASV) measures labile species, so the approximation involved in interpretation as simple inorganic species, from which free ion activities can be derived, should be recognized. Diffusive gradients in thin-films also measures labile species, but it is applicable to a much wider range of metals than ASV. It requires larger volumes of solution, but it can be used directly on the whole soil where it also measures the metal that can be rapidly supplied to solution. Other techniques such as permeable liquid membranes have yet to be used for measurements on soil solution. All of these methods have strength and weaknesses, and measure different aspects of speciation. Knowledge of the availability of the metals to biota is likely to be best advanced by the critical use of one or more of these speciation methods with a thorough understanding of exactly what is being measured.

Anthropogenic metal enrichment of snow and soil in north-eastern European Russia

Trace metal composition of winter snowpack, snow-melt filter residues and top-soil samples were determined along three transects through industrial towns in the Usa basin, North-East Russia: Inta, Usinsk and Vorkuta. Snow was analysed for Ag, Al, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn using ICP-MS (Ca and K by F-AAS for Vorkuta only), pH and acidity/alkalinity. Filter residues were analysed for: Al, Ba, Ca, Cd, Cu, K, Mg, Mn, Ni, Pb, Sr and Zn using F-AAS and GF-AAS; top-soil samples were analysed for Ba, Cu, Mg, Mn, Na, Ni, Pb, Sr, Zn using F-AAS. Results indicate elevated concentrations of elements associated with alkaline combustion ash around the coal mining towns of Vorkuta and Inta. There is little evidence of deposition around the gas and oil town of Usinsk. Atmospheric deposition in the vicinity of Vorkuta, and to a lesser extent Inta, added significantly to the soil contaminant loading as a result of ash fallout. Acid deposition was associated with pristine areas whereas alkaline combustion ash near to emission sources more than compensated for the acidity caused by SO2.

The toxicity of cadmium to barley plants as affected by complex formation with humic acid

An ‘alternating solution’ culture method was used to study the effects of chloride ions and humic acid (HA) on the uptake of cadmium by barley plants. The plants were transferred periodically between a nutrient solution and a test solution containing one of four levels of HA (0, 190, 569 or 1710 μg cm−3) and one of five levels of Cd (0, 0.5, 1.0, 2.5 or 5.0 μg cm−3) in either a 0.006M NaNO3 or 0.006M NaCl medium. Harvest and analysis of shoots and roots was after nineteen days. The distribution of Cd in the test solutions between Cd2+, CdCl+ and HA-Cd was determined in a separate experiment by dialysis equilibrium.In the nitrate test solutions Cd uptake was clearly controlled by Cd2+ concentration and was therefore reduced by HA complex formation. In the absence of HA, chloride suppressed Cd uptake indicating that Cd2+ was the preferred species. However complex formation with Cl− enhanced uptake when HA was present because of an increase in the concentration of inorganic Cd species relative to the nitrate system.The ratio root-Cd/shoot-Cd remained at about 10 across a wide range of shoot-Cd concentrations, from about 3 μg g−1 (sub-toxic) up to 85 μg g−1 (80% yield reduction). The ability of the barley plants to accumulate ‘non-toxic’ Cd in their roots was thus very limited. Humic acid also had no effect on Cd translocation within the plant and the root/shoot weight ratio did not vary with any treatment.At shoot-Cd concentrations in excess of 50 μg g−1, K, Ca, Cu and Zn uptake was reduced, probably the result of root damage rather than a specific ion antagonism. The highest concentration of HA also lowered Fe and Zn uptake and there was a toxic effect with increasing HA concentration at Cd=0. However the lowest HA level, comparable with concentrations found in mineral soil solutions, only reduced yield (in the absence of Cd) by <5% while lowering Cd uptake across the range of Cd concentrations by 66%–25%.